CN102718588A - Compound fertilizer produced by tubular reaction and method for preparing compound fertilizer - Google Patents
Compound fertilizer produced by tubular reaction and method for preparing compound fertilizer Download PDFInfo
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Abstract
The invention discloses a compound fertilizer produced by tubular reaction and a method for preparing the compound fertilizer. The compound fertilizer contains trace elements and ammonium polyphosphate with the degree of polymerization not larger than 10, and the problem that the phosphate fertilizer cannot be applied with the trace elements is solved. The compound fertilizer contains the ammonium polyphosphate and the trace elements simultaneously, the ammonium polyphosphate and the trace elements such as zinc and ferrum can generate chelate which is completely water-soluble to supply the phosphate fertilizer and the trace elements to plants simultaneously. Phosphoric acid and ammonia directly generate polyphosphate in a tubular reactor, the generated polyphosphate can be directly granulated, and nitrogenous fertilizer, potash fertilizer and the trace elements can be added to the polyphosphate to be granulated. The process is simple, and production cost is reduced.
Description
Technical field
The present invention relates to composite fertilizer that a kind of pipe reaction produces and preparation method thereof, be specifically related to composite fertilizer of composite fertilizer that a kind of tubular reactor-rotary drum prilling process produces and preparation method thereof and a kind of high tower pipe reaction explained hereafter and preparation method thereof.
Background technology
Ammonium polyphosphate is claimed ammonium polyphosphate or polycondensation ammonium phosphate (being called for short APP) again, and ammonium polyphosphate is not a kind of simplification compound, but one type of chemical constitution is similar, structure and the material of some difference is arranged again in nature.Nineteen sixty-five, U.S. Monsanto Company at first succeeded in developing.Ammonium polyphosphate is nonpoisonous and tasteless, does not produce etchant gas, and water absorbability is little, and thermostability is high, is a kind of non-halogen fire retardant of excellent property.In early 1970s, beginning mass production such as Japanese, preceding West Germany, the FSU is used comparatively general at present.China develops this series products since the eighties in 20th century, and there are tens families in manufacturing enterprise, mainly as fire retardant.
Ammonium polyphosphate is the poly-phosphate of a kind of N of containing and P, by its polymerization degree can be divided into oligomeric, in gather and height gathers 3 kinds, its polymerization degree highly water-soluble more is more little, otherwise then water-soluble big more.Can be divided into crystallization shape and amorphous by its structure, the crystal form ammonium polyphosphate is a long-chain shape water-insoluble salt.The general molecular formula of ammonium polyphosphate is (NH
4)
(n+2)P
nO
(3n+1), when n less than 20 the time, for water-soluble; When n greater than 20 the time, be insoluble.
Along with the development of technology, ammonium polyphosphate has progressed into the production of compound fertilizer and liquid fertilizer, particularly is used widely in developed country.Early 1970s, U.S. TVA has developed with commodity phosphoric acid by wet process (54%P
2O
5, massfraction) and produce ammonium polyphosphate basis liquid fertilizer, just phosphoric acid by wet process is condensed into peroxophosphoric acid, in tubular reactor,, generate the high density ammonium polyphosphate with ammonia react, adding water cooling generation grade is the liquid fertilizer product of 10-34-0.The basis liquid fertilizer can be produced liquid compound fertilizer with nitrogenous fertilizer, potash fertilizer.The TVA of the U.S., seldom is used in the solid fertilizer as generally being to be used in solution fertilizer or suspension fertilizer in the research of fertilizer ammonium polyphosphate.
Generally is tubular reactor-tempering tank molectron method at the existing production fertilizer of the U.S. with polyphosphoric acid solution; Because the raw material of this method utilization is a peroxophosphoric acid; So want earlier phosphoric acid to be transformed into peroxophosphoric acid, and phosphoric acid is transformed into the cost that peroxophosphoric acid can increase acid, increases technology difficulty.
China is the enterprise of rarer professional production ammonium polyphosphate fertilizer at present; Domestic phosphate fertilizer of the prior art generally all is contain orthophosphoric acid salt many; But orthophosphoric acid salt can generate deposition with the various trace elements reaction; And but these trace elements by chance are that plant is needed, in case generate deposition with orthophosphoric acid salt, plant just can't absorb these insolubless.Moreover, if there are sedimentary words can stop up the shower nozzle of irrigation conduit in the water-soluble fertilizer.Because domestic phosphate fertilizer of the prior art generally all is contain orthophosphoric acid salt many, therefore, trace element generally can not be used with phosphate fertilizer together at home at present.
Trace element is meant a kind of chemical element that occurring in nature content is very low.The part trace element has biological significance, is that the plant and animal normal growth is necessary with life, is called " essential trace element " perhaps " micro-nutrient ", is called for short usually " trace element ".Essential trace element has very strong specificity in the intravital effect of plant and animal, is can not lack with irreplaceable, and when undersupply, plant often shows specific shortage symptom, and crop yield reduces, and downgrade possibly have no harvest when serious.And apply trace element fertilizer, and helping the raising of output, this is confirmed by scientific experimentation and production test.
Quantitative theory, for crop, content is called " trace element " between the essential nutrient element of 0.2～200 milligram/kilogram (by dry restatement).Up to the present, confirm that the crop trace elements necessary has boron, manganese, copper, zinc, molybdenum, iron, chlorine etc.These elements manufacture fertilizer through factory, just are called trace element fertilizer, belong to zinc fertilizer like Zinc Sulphate Heptahydrate, and borax, boric acid belong to boron fertilizer, and manganous sulfate belongs to manganese fertilizer, and ammonium molybdate belongs to molydbenum fertilizer, and copper sulfate belongs to copper fertilizer, and ferrous sulfate belongs to iron fertilizer etc.
Compare with orthophosphoric acid salt, some metallic element of ammonium polyphosphate ability chelating therefore can blending part trace element (like iron, zinc etc.) in containing the fertilizer of ammonium polyphosphate.But because the deficiency of prior art; The domestic enterprise that rarely has production to contain the composite fertilizer of ammonium polyphosphate; And mostly external ammonium polyphosphate is liquid fertilizer, also seldom does solid fertilizer, because the liquid fertilizer packed and transported is also inconvenient; Thereby the fertilizer finished product transportation cost that causes containing ammonium polyphosphate is too high, and is not suitable for China's national situation.
Summary of the invention
The composite fertilizer that the object of the present invention is to provide a kind of pipe reaction to produce, this composite fertilizer includes the polymerization degree and is not more than 10 short chain ammonium polyphosphate and trace element, has solved the problem that phosphate fertilizer in the domestic prior art can not be used with trace element together.
For realizing the foregoing invention purpose, the present invention adopts following technical scheme:
The composite fertilizer that a kind of pipe reaction is produced contains the trace element and the polymerization degree and is not more than 10 short chain ammonium polyphosphate in the said composite fertilizer.
Preferably, said trace element is the one or more combination in zinc, copper, iron and the manganese.
Another object of the present invention is to provide produce and contain the polymerization degree and be not more than 10 the short chain ammonium polyphosphate and the method for the composite fertilizer of trace element.
A kind of working method of described composite fertilizer may further comprise the steps:
Step 1: phosphoric acid, sulfuric acid, ammonia and washing water are pressed mass ratio (0.5-1): (0.02-0.5): (0.06-0.41): (0-0.2) feed in the pipeline reactor; Phosphoric acid, sulfuric acid and the ammonia temperature of reaction that reacts is 200-300 ℃ and generates the mixed slurry that sulfur acid ammonium and the polymerization degree are not more than 10 ammonium polyphosphate that the water in the raw material is become steam by reacting heat evaporation;
Step 2: mixed slurry feeds rotary drum granulator; Potash fertilizer, nitrogenous fertilizer and trace element get into lift through potash fertilizer feeder, nitrogenous fertilizer feeder and micro-feeder respectively; Feed again in the rotary drum granulator mix with mixed slurry, granulation, obtain compound fertilizer granules; Wherein said steam separates with mixed slurry in tablets press;
Step 3: compound fertilizer granules is passed into cooling cylinder cooling, sieves through molecular sieve again, at last to qualified compound fertilizer granules apply powder, the oil spout parcel can obtain said composite fertilizer.
Preferably, the quality percentage composition of the phosphoric acid described in the step 1 is with P
2O
5Count 47%-54%, temperature is 100 ~ 140 ℃; Said vitriolic mass percent is 93%-98%, and temperature is a normal temperature, and the temperature of ammonia is a normal temperature.
Preferably, the phosphoric acid in the step 1 feeds tubular reactor after getting into the phosphoric acid heater heats through the phosphoric acid pump; Sulfuric acid gets into tubular reactor through the sulfuric acid pump.
Preferably, after the separating obtained steam feeding washing device washing of rotary drum granulator removed the little ammonia in the devaporation, washing water fed tubular reactor then, steam discharging or collection utilization in the step 2.
Preferably, the underproof compound fertilizer granules in screening back gets into the granulation again of lift, tablets press at last through crusher in crushing, again through returning charge lift entering returning charge feeder in the step 3.
The another kind of working method of described composite fertilizer said method comprising the steps of:
Step 1: phosphoric acid, sulfuric acid, ammonia and washing water are pressed mass ratio (0.5-1): (0.02-0.5): (0.06-0.41): (0-0.2) feed in the pipeline reactor; Phosphoric acid, sulfuric acid and the ammonia temperature of reaction that reacts is 200-300 ℃ and generates the mixed slurry that sulfur acid ammonium and the polymerization degree are not more than 10 ammonium polyphosphate that the water in the raw material is become steam by reacting heat evaporation;
Step 2: mixed slurry and steam are passed into vapour separator, mixed slurry and vapor removal;
Step 3: mixed slurry is fed slurry vessel, add urea, an ammonium nitrate, solid sylvite and trace element, the heat through steam heats slurry vessel, makes the material fusion, obtains melting charge slurry; Wherein urea and an ammonium nitrate are only selected an adding;
Step 4: melting charge slurry is fed the granulation of high tower pellatizer machine, obtain compound fertilizer granules;
Step 5: compound fertilizer granules is transported to cooling cylinder cooling, sieves again, at last to qualified compound fertilizer granules apply powder, the oil spout parcel can obtain said composite fertilizer.
Preferably, the quality percentage composition of the phosphoric acid described in the step 1 is with P
2O
5Count 47%-54%, temperature is 100-140 ℃; Said vitriolic mass percent is 93%-98%, and temperature is a normal temperature, and the temperature of ammonia is a normal temperature.
Preferably, the underproof compound fertilizer granules in screening back mixes granulation again through crusher in crushing, again through returning charge lift entering slurry vessel in the step 5 with melting charge slurry.
Beneficial effect of the present invention:
(1) phosphoric acid and ammonia directly generate ammonium polyphosphate in the inventive method in tubular reactor, and the directly granulation of the ammonium polyphosphate of generation also can be added nitrogenous fertilizer, potash fertilizer and trace element and carry out granulation, and technology is simple, and production cost reduces.
(2) composite fertilizer of the present invention is a solid fertilizer, and transportation cost reduces, and promotes more easily.
(3) can contain ammonium polyphosphate and trace element simultaneously in the composite fertilizer of the present invention, ammonium polyphosphate can generate water-soluble inner complex fully with trace elements such as zinc, iron, can replenish phosphate fertilizer and trace element simultaneously to plant.
(4) in the inventive method through phosphoric acid being preheated, uses high-concentration sulfuric acid and phosphoric acid, and the great amount of heat energy of utilizing sour ammonia react to emit, save energy.
Description of drawings
Fig. 1 is the technological process of production figure of composite fertilizer of the present invention;
Fig. 2 is the another kind of technological process of production figure of composite fertilizer of the present invention.
Embodiment
Trace element is meant a kind of chemical element that occurring in nature content is very low.The part trace element has biological significance, is that the plant and animal normal growth is necessary with life, is called " essential trace element " perhaps " micro-nutrient ", is called for short usually " trace element ".Essential trace element has very strong specificity in the intravital effect of plant and animal, is can not lack with irreplaceable, and when undersupply, plant often shows specific shortage symptom, and crop yield reduces, and downgrade possibly have no harvest when serious.And apply trace element fertilizer, and helping the raising of output, this is confirmed by scientific experimentation and production test.
Quantitative theory, for crop, content is called " trace element " between the essential nutrient element of 0.2～200 milligram/kilogram (by dry restatement).Up to the present, confirm that the crop trace elements necessary has boron, manganese, copper, zinc, molybdenum, iron, chlorine etc.These elements manufacture fertilizer through factory, just are called trace element fertilizer, belong to zinc fertilizer like Zinc Sulphate Heptahydrate, and borax, boric acid belong to boron fertilizer, and manganous sulfate belongs to manganese fertilizer, and ammonium molybdate belongs to molydbenum fertilizer, and copper sulfate belongs to copper fertilizer, and ferrous sulfate belongs to iron fertilizer etc.
Trace element can add a kind ofly also can add several kinds simultaneously, and concrete combination can determine according to the soil practical situation.
Below in conjunction with embodiment the present invention is done further explanation and explanation, following examples do not constitute any limitation the present invention.
Embodiment 1: specification is a 11-50-0-Zn composite fertilizer
Step 1: the quality percentage composition that will be heated to 120 ℃ is 47% (with P
2O
5Meter) to be 98% sulfuric acid with flow, the quality percentage composition of 11.17t/h feed in the pipeline reactor with flow, the ammonia of 0.5t/h with the flow of 1.43t/h phosphoric acid simultaneously; Temperature of reaction is 232 ℃, obtains the mixed slurry and the steam of sulfur acid ammonium and ammonium polyphosphate;
Step 2: mixed slurry feeds rotary drum granulator, and Zinc Sulphate Monohydrate gets into lift through micro-feeder simultaneously, feed in the rotary drum granulator with the amount of 0.056t/h again mix with mixed slurry, granulation, obtain compound fertilizer granules; Wherein said steam separates with mixed slurry in tablets press;
Step 3: compound fertilizer granules is passed into cooling cylinder cooling, sieves through molecular sieve again, at last to qualified compound fertilizer granules apply powder, the oil spout parcel can obtain said composite fertilizer; Wherein underproof compound fertilizer granules is through crusher in crushing, again through returning charge lift entering returning charge feeder, lift, and the circulation returning charge gets into tablets press drum granulating tube with the amount of 30.2t/h.
Complex fertilizer product to gained detects: the quality percentage composition of nitrogen is 11%; The quality percentage composition of Vanadium Pentoxide in FLAKES is 50%, and wherein to account for the per-cent of total Vanadium Pentoxide in FLAKES be 28% to ammonium polyphosphate, and mean polymerisation degree is 2.3; The quality percentage composition of zinc is 0.2%.
Embodiment 2: specification is a 8-24-24-Cu composite fertilizer
Step 1: the quality percentage composition that will be heated to 110 ℃ is 47% (with P
2O
5Meter) to be 98% sulfuric acid with flow, the quality percentage composition of 10.3t/h feed in the pipeline reactor with flow, the ammonia of 2.6t/h with the flow of 1.67t/h phosphoric acid simultaneously; Temperature of reaction is 243 ℃, obtains the mixed slurry and the steam of sulfur acid ammonium and ammonium polyphosphate;
Step 2: mixed slurry feeds rotary drum granulator, simultaneously with the cupric sulfate pentahydrate of 0.39t/h and be mix with mixed slurry in the Repone K feeding rotary drum granulator of 8t/h, granulation, obtain compound fertilizer granules; Wherein said steam separates with mixed slurry in tablets press;
Step 3: compound fertilizer granules is passed into cooling cylinder cooling, sieves through molecular sieve again, at last to qualified compound fertilizer granules apply powder, the oil spout parcel can obtain said composite fertilizer; Wherein underproof compound fertilizer granules is through crusher in crushing, again through returning charge lift entering returning charge feeder, lift, and the circulation returning charge gets into tablets press drum granulating tube with the amount of 30t/h.
Complex fertilizer product to gained detects: the quality percentage composition of nitrogen is 8%; The quality percentage composition of Vanadium Pentoxide in FLAKES is 24%, and wherein to account for the per-cent of total Vanadium Pentoxide in FLAKES be 37% to ammonium polyphosphate, and mean polymerisation degree is 3.2; The quality percentage composition of potassium oxide is 24%; The quality percentage composition of copper is 0.5%.
Embodiment 3: specification is a 18-18-18-Zn composite fertilizer
Step 1: the quality percentage composition that will be heated to 120 ℃ is 47% (with P
2O
5Meter) to be 98% sulfuric acid with flow, the quality percentage composition of 16.09t/h feed in the pipeline reactor with flow, the ammonia of 0.72t/h with the flow of 2.1t/h phosphoric acid simultaneously; 223 ℃ of reactions down, obtain the mixed slurry and the steam of sulfur acid ammonium and ammonium polyphosphate;
Step 2: mixed slurry and steam are passed into vapour separator, mixed slurry and vapor removal;
Step 3: mixed slurry is fed slurry vessel, simultaneously the vitriolate of tartar of the urea of 12.8t/h, 15.2t/h and the Zinc Sulphate Monohydrate of 0.22t/h are added in the slurry vessel, the heat through steam heats slurry vessel, makes all material fusions, obtains melting charge slurry;
Step 4: melting charge slurry is fed the granulation of high tower pellatizer machine, obtain compound fertilizer granules;
Step 5: compound fertilizer granules is passed into cooling cylinder cooling, sieves through molecular sieve again, at last to qualified compound fertilizer granules apply powder, the oil spout parcel can obtain said composite fertilizer; Wherein underproof compound fertilizer granules mixes granulation again through crusher in crushing, again through returning charge lift entering slurry vessel with melting charge slurry.
Complex fertilizer product to gained detects: the quality percentage composition of nitrogen is 18%; The quality percentage composition of Vanadium Pentoxide in FLAKES is 18%, and wherein to account for the per-cent of total Vanadium Pentoxide in FLAKES be 24% to ammonium polyphosphate, and mean polymerisation degree is 2.0; The quality percentage composition of potassium oxide is 18%; The quality percentage composition of zinc is 0.4%.
Embodiment 4:
Specification is a 11-50-0-Mn composite fertilizer
Step 1: the quality percentage composition that will be heated to 120 ℃ is 47% (with P
2O
5Meter) to be 98% sulfuric acid with flow, the quality percentage composition of 11.17t/h feed in the pipeline reactor with flow, the ammonia of 0.48t/h with the flow of 1.43t/h phosphoric acid simultaneously; Temperature of reaction is 232 ℃, obtains the mixed slurry and the steam of sulfur acid ammonium and ammonium polyphosphate;
Step 2: mixed slurry feeds rotary drum granulator, and manganous sulfate gets into lift through micro-feeder, feed in the rotary drum granulator with the amount of 0.08t/h again mix with mixed slurry, granulation, obtain compound fertilizer granules; Wherein said steam separates with mixed slurry in tablets press;
Step 3: compound fertilizer granules is passed into cooling cylinder cooling, sieves through molecular sieve again, at last to qualified compound fertilizer granules apply powder, the oil spout parcel can obtain said composite fertilizer; Wherein underproof compound fertilizer granules is through crusher in crushing, again through returning charge lift entering returning charge feeder, lift, and the circulation returning charge gets into tablets press drum granulating tube with the amount of 30.2t/h.
Complex fertilizer product to gained detects: the quality percentage composition of nitrogen is 11%; The quality percentage composition of Vanadium Pentoxide in FLAKES is 50%, and wherein to account for the per-cent of total Vanadium Pentoxide in FLAKES be 28% to ammonium polyphosphate, and mean polymerisation degree is 2.3; The quality percentage composition of manganese is 0.2%.
Complex fertilizer product among the above embodiment; Survey phosphorus the method for quality percentage composition be the method for the GB 8573-2010 " mensuration of available phosphorus content in the composite fertilizer " of usefulness; The method of surveying the quality percentage composition of nitrogen is the GB8572-2010 " mensuration of total nitrogen content in the composite fertilizer " of usefulness, and that the method for the survey polymerization degree is used is GB/T9984.3-2004.
According to the announcement and the instruction of above-mentioned specification sheets, those skilled in the art in the invention can also change and revise above-mentioned embodiment.Therefore, the specific embodiment that discloses and describe above the present invention is not limited to also should fall in the protection domain of claim of the present invention modifications and changes more of the present invention.In addition, although used some specific terms in this specification sheets, these terms are explanation for ease just, the present invention is not constituted any restriction.
Claims (10)
1. the composite fertilizer that pipe reaction is produced is characterized in that: contain the trace element and the polymerization degree in the said composite fertilizer and be not more than 10 short chain ammonium polyphosphate.
2. composite fertilizer according to claim 1 is characterized in that: said trace element is one or several in zinc, copper, iron and the manganese.
3. the working method of claim 1 or 2 described composite fertilizers is characterized in that, said method comprising the steps of:
Step 1: phosphoric acid, sulfuric acid, ammonia and washing water are pressed mass ratio (0.5-1): (0.02-0.5): (0.06-0.41): (0-0.2) feed in the pipeline reactor; Phosphoric acid, sulfuric acid and the ammonia temperature of reaction that reacts is 200 ~ 300 ℃ and generates the mixed slurry that sulfur acid ammoniums and the polymerization degree are not more than 10 ammonium polyphosphate that the water in the raw material is become steam by reacting heat evaporation;
Step 2: mixed slurry feeds rotary drum granulator; Potash fertilizer, nitrogenous fertilizer and trace element get into lift through potash fertilizer feeder, nitrogenous fertilizer feeder and micro-feeder respectively; Feed again in the rotary drum granulator mix with mixed slurry, granulation, obtain compound manure; Wherein said steam separates with mixed slurry in tablets press;
Step 3: compound fertilizer granules is passed into cooling cylinder cooling, sieves through sieve again, at last to qualified compound fertilizer granules apply powder, the oil spout parcel can obtain said composite fertilizer.
4. composite fertilizer producing process according to claim 3 is characterized in that: the quality percentage composition of the phosphoric acid described in the step 1 is with P
2O
5Count 47%-54%, temperature is 100-140 ℃; Said vitriolic mass percent is 93%-98%, and temperature is a normal temperature, and the temperature of ammonia is a normal temperature.
5. composite fertilizer producing process according to claim 3 is characterized in that: the phosphoric acid in the step 1 feeds tubular reactor after getting into the phosphoric acid heater heats through the phosphoric acid pump; Sulfuric acid gets into tubular reactor through the sulfuric acid pump.
6. composite fertilizer producing process according to claim 3; It is characterized in that: feed after the washing device washing removes the little ammonia in the devaporation through the separating obtained steam of rotary drum granulator in the step 2; Washing water feed tubular reactor then, and steam discharging or collection utilize.
7. composite fertilizer producing process according to claim 3 is characterized in that: the underproof compound fertilizer granules in screening back gets into the granulation again of lift, tablets press at last through crusher in crushing, again through returning charge lift entering returning charge feeder in the step 3.
8. the working method of claim 1 or 2 described composite fertilizers is characterized in that, said method comprising the steps of:
Step 1: phosphoric acid, sulfuric acid, ammonia and washing water are pressed mass ratio (0.5-1): (0.02-0.5): (0.06-0.41): (0-0.2) feed in the pipeline reactor; Phosphoric acid, sulfuric acid and the ammonia temperature of reaction that reacts is 200-300 ℃ and generates the mixed slurry that sulfur acid ammonium and the polymerization degree are not more than 10 ammonium polyphosphate that the water in the raw material is become steam by reacting heat evaporation;
Step 2: mixed slurry and steam are passed into vapour separator, mixed slurry and vapor removal;
Step 3: mixed slurry is fed slurry vessel, add urea, an ammonium nitrate, solid sylvite and trace element, the heat through steam heats slurry vessel, makes the material fusion, obtains melting charge slurry; Wherein urea and an ammonium nitrate are only selected an adding;
Step 4: melting charge slurry is fed the granulation of high tower pellatizer machine, obtain compound fertilizer granules;
Step 5: compound fertilizer granules is transported to cooling cylinder cooling, sieves again, at last to qualified compound fertilizer granules apply powder, the oil spout parcel can obtain said composite fertilizer.
9. composite fertilizer producing process according to claim 8 is characterized in that: the quality percentage composition of the phosphoric acid described in the step 1 is with P
2O
5Count 47%-54%, temperature is 100-140 ℃; Said vitriolic mass percent is 93%-98%, and temperature is a normal temperature, and the temperature of ammonia is a normal temperature.
10. composite fertilizer producing process according to claim 8 is characterized in that: the underproof compound fertilizer granules in screening back mixes granulation again through crusher in crushing, again through returning charge lift entering slurry vessel in the step 5 with melting charge slurry.
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| CN103787726B (en) * | 2014-02-21 | 2015-06-03 | 山东泰宝生物科技股份有限公司 | Ammonium polyphosphate water soluble fertilizer and preparation method thereof |
| CN103787726A (en) * | 2014-02-21 | 2014-05-14 | 山东泰宝生物科技股份有限公司 | Ammonium polyphosphate water soluble fertilizer and preparation method thereof |
| CN104261932A (en) * | 2014-09-17 | 2015-01-07 | 湖北祥云(集团)化工股份有限公司 | Zinc-containing compound fertilizer and preparation method thereof |
| CN104261932B (en) * | 2014-09-17 | 2016-03-30 | 湖北祥云(集团)化工股份有限公司 | A kind of containing zinc composite fertilizer and preparation method thereof |
| CN104291307A (en) * | 2014-09-19 | 2015-01-21 | 贵州大学 | Method for preparing monocalcium phosphate and fertilizer for garlic |
| CN104555969A (en) * | 2014-09-19 | 2015-04-29 | 贵州大学 | Method for preparing monocalcium phosphate and co-producing special fertilizer for sweet potatoes |
| CN104229766B (en) * | 2014-09-19 | 2017-02-08 | 贵州开磷集团股份有限公司 | Production method for preparing monocalcium phosphate byproduct used as special fertilizer for chives |
| CN104229766A (en) * | 2014-09-19 | 2014-12-24 | 贵阳中化开磷化肥有限公司 | Production method for preparing monocalcium phosphate byproduct used as special fertilizer for chives |
| CN104555969B (en) * | 2014-09-19 | 2016-08-24 | 贵州大学 | A kind of method preparing calcium dihydrogen phosphate co-production ground melon specific fertilizer |
| CN104355734A (en) * | 2014-10-24 | 2015-02-18 | 瓮福（集团）有限责任公司 | Production method of ammonium sulfate-ammonium phosphate composite fertilizer |
| CN104529623A (en) * | 2014-12-10 | 2015-04-22 | 中化化肥有限公司成都研发中心 | Agricultural ammonium polyphosphate capable of being chelated with medium trace elements and preparation method of agricultural ammonium polyphosphate |
| CN104529591A (en) * | 2014-12-17 | 2015-04-22 | 贵州开磷（集团）有限责任公司 | Method and device for preparing bulk blending fertilizer by using nitro nitrogen and phosphorus master batches |
| CN104496608A (en) * | 2014-12-29 | 2015-04-08 | 深圳市芭田生态工程股份有限公司 | Ammonium polyphosphate chelate fertilizer as well as preparation method and application thereof |
| CN105776167A (en) * | 2015-04-02 | 2016-07-20 | 贵州芭田生态工程有限公司 | Polyphosphate and preparation method thereof |
| CN105272477A (en) * | 2015-11-17 | 2016-01-27 | 深圳市芭田生态工程股份有限公司 | Water-soluble ammonium polyphosphate NPK compound fertilizer and preparation method thereof |
| CN105481515A (en) * | 2015-12-31 | 2016-04-13 | 王丰登 | Production method of compound fertilizer containing poly-magnesium phosphate |
| CN108440048A (en) * | 2016-08-31 | 2018-08-24 | 史丹利农业集团股份有限公司 | A kind of nitre sulfenyl ammonium polyphosphate tower granulation full water soluble fertilizer and its manufacturing method |
| CN109704818A (en) * | 2017-10-25 | 2019-05-03 | 四川大学 | DAP compound fertilizer and preparation method thereof |
| CN109704818B (en) * | 2017-10-25 | 2020-06-30 | 四川大学 | DAP compound fertilizer and preparation method thereof |
| CN108117460A (en) * | 2018-01-31 | 2018-06-05 | 河南博联农业研究院有限公司 | A kind of water soluble fertilizer for synergy of losing weight and preparation method thereof |
| CN108727133A (en) * | 2018-06-13 | 2018-11-02 | 贵阳开磷化肥有限公司 | A kind of preparation method of salt-soda soil special complex fertilizer |
| CN112979386A (en) * | 2019-12-13 | 2021-06-18 | 新乡市威远化工新技术有限公司 | Low-polymerization-degree ammonium polyphosphate particle multi-component compound fertilizer and preparation method thereof |
| CN111574273A (en) * | 2020-04-28 | 2020-08-25 | 贵州芭田生态工程有限公司 | Preparation method of poly ammonium phosphate calcium nitrate magnesium fertilizer and poly ammonium phosphate calcium nitrate magnesium fertilizer |
| CN113248322A (en) * | 2021-05-25 | 2021-08-13 | 贵州川恒化工股份有限公司 | Preparation method of soluble medium-trace element fertilizer |
| CN114560744A (en) * | 2022-03-14 | 2022-05-31 | 云南云天化股份有限公司 | Method for preparing polymorphic phosphorus compound fertilizer |
| CN114560744B (en) * | 2022-03-14 | 2023-12-05 | 云南云天化股份有限公司 | Method for preparing multi-form phosphorus compound fertilizer |
| CN115784798A (en) * | 2022-11-14 | 2023-03-14 | 云南云天化股份有限公司 | Method for producing sulfur-containing compound fertilizer by using low-quality phosphoric acid |
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